BRPI0620351B1 - Aqueous Dispersion of Cellular Reactive Glue Agent, Method for Preparing a Watery Dispersion, Use of Aqueous Cellular Reactive Glue Dispersion, and Process for the Production of PAPER - Google Patents

Abstract

Paper collage. The present invention relates to an aqueous dispersion of cellulose-reactive sizing agent containing an acid anhydride, an anionic polyelectrolyte and a nitrogen-containing organic compound which is ummine or its quaternary ammonium having a molecular weight of less than 180 and / or having one or more hydroxyl groups. The invention further relates to a method for the preparation of an aqueous dispersion of cellulose reactive sizing agent comprising dispersing an acid anhydride in an aqueous phase in the presence of an anionic polyelectrolyte and a nitrogen-containing organic compound which is an amine. or its quaternary ammonium having a molecular weight of less than 180 and / or having one or more hydroxyl groups. The invention also relates to the use of the aqueous dispersion of cellulose reactive sizing agent as a stock sizing agent or surface sizing agent in papermaking. The invention further relates to a papermaking process comprising adding the aqueous dispersion of the cellulose reactive sizing agent to an aqueous cellulosic suspension.

Description

(54) Title: WATER DISPERSION OF REACTIVE GLUING AGENT WITH CELLULOSE, METHOD FOR PREPARING A WATER DISPERSION, USE OF WATER DISPERSION OF REACTIVE GLUING AGENT WITH CELLULOSE, AND PROCESS FOR PAPER PRODUCTION (51) Int.CI. : D21H 21/16 (30) Unionist Priority: 12/21/2005 EP 05 112656.3 (73) Holder (s): KEMIRA OYJ (72) Inventor (s): HANS JOHANSSON-VESTIN; JONAS LIESÉN; MARIE TURUNEN; JAN EMANUELSSON

Descriptive Report of the Invention Patent for WATER DISPERSION OF REACTIVE GLUING AGENT WITH CELLULOSE, METHOD FOR THE PREPARATION OF A WATER DISPERSION, USE OF THE WATER DISPERSION OF REACTIVE GLUE AGENT WITH CE5 LULOSE, AND PROCESS FOR PAPER PRODUCTION.

Field of the Invention

The present invention relates to the sizing of paper, more specifically to aqueous dispersions of sizing agent reactive with cellulose and its preparation and use. Background of the Invention

Cellulose reactive sizing agents such as those based on succinic alkenyl anhydride (ASA) are widely used in paper making at neutral or slightly alkaline stock pH's to give paper and cardboard some degree of resistance to wetting and penetration by aqueous liquids. Paper sizing based on cellulose reactive sizing agents is generally provided in the form of dispersions containing an aqueous phase and finely divided particles or droplets of the sizing agent dispersed therein. Dispersions are generally prepared with the aid of a dispersant system consisting of an anionic compound, for example, sodium lignosulfonate, in combination with a high molecular weight amphoteric or cationic polymer, for example, a cationic starch polymer, polyamine, polyamidoamine or vinyl addition.

WO 96/17127 describes aqueous dispersions which comprise a sizing agent reactive with cellulose and colloidal anionic aluminum modified silica particles.

WO 97/31152 describes aqueous dispersions that comprise a reactive sizing agent and an anionic microparticle material. The dispersions can also contain no more than 2% (by weight based on the weight of reactive sizing agent) surfactant. The surfactant can be non-ionic or anionic.

WO 98/33979 A1 describes an aqueous dispersion of cellulose-reactive sizing agent and a dispersing system comprising a cationic organic compound and an anionic stabilizer.

Despite the fact that considerable improvements have been achieved 870160044726, of 17/08/2016, p. 12/3

- In view of the preparation, properties and performance of aqueous dispersions of succinic alkenyl anhydride, there are still some technical problems associated with the use of such dispersions. Generally, dispersions of alkenyl succinic anhydride exhibit poor stability, which evidently leads to difficulties in handling the dispersions, however, in storage and use. An additional drawback is that aqueous dispersions cannot be stored for longer periods of time, because alkenyl succinic anhydride easily hydrates and then becomes ineffective as a sizing agent.

In this way, alkenyl succinic anhydride is generally delivered to paper mills as a liquid, which is then dispersed before use as a sizing agent and the dispersion obtained is generally used within 2 hours to avoid problems of insufficient stability and loss of bonding efficiency. The equipment used to prepare dispersions provides high shear forces to be able to free surfaces and produce dispersions having adequate particle bonding. Such equipment is often both complicated and expensive, and due to the high shear forces it usually requires a considerable amount of energy.

It is an object of the present invention to provide an aqueous dispersion of cellulose-reactive sizing agent that can be easily prepared using low shear forces and low energy consumption. It is a further object of the present invention to provide an aqueous dispersion of cellulose-reactive sizing agent showing improved sizing stability and efficiency. Additional goals will appear below.

Summary of the Invention

The invention relates to an aqueous dispersion of cellulose-reactive sizing agent containing an acid anhydride, an anionic polyelectrolyte and a nitrogen-containing organic compound that is an amine or its quaternary ammonium having a molecular weight of less than 180 and / or having one or more hydroxyl groups.

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The invention further relates to a method for the preparation of an aqueous dispersion of cellulose-reactive sizing agent which comprises dispersing an acid anhydride in an aqueous phase in the presence of an anionic polyelectrolyte and an organic compound containing nitro5 genius which is a amine or its quaternary ammonium having a molecular weight of less than 180 and / or having one or more hydroxyl groups.

The invention also relates to the use of the aqueous dispersion of cellulose-reactive sizing agent as a stock sizing agent or surface sizing agent in the production of paper. The invention further relates to a process for the production of paper which comprises adding the aqueous dispersion of cellulose-reactive sizing agent to an aqueous cellulosic suspension and removing water from the suspension obtained in a grid as well as a process for the production of paper comprising application of the aqueous dispersion of cellulose-reactive sizing agent to a cellulosic web.

Detailed Description of the Invention

In accordance with the present invention, it has been found that improved paper sizing can be achieved using the present aqueous dispersion of cellulose-reactive sizing agent. It has also been found that the present dispersions show better stability over conventional dispersions. In addition, it has been found that lower shear forces can be used to prepare the present aqueous dispersions compared to when preparing conventional aqueous dispersions of cellulose-reactive sizing agent. In this way the present invention makes it possible to use simple, energy-saving and investment equipment by creating low shear forces, such as, for example, static mixers. The present invention then offers substantial economic and technical benefits.

The cellulose-reactive sizing agent according to the invention can be selected from any anhydride-based sizing agent known in the art. Suitably, the sizing agent is a hydrophobic acid anhydride. Suitable hydrophobic acid hydrides can be characterized by the general formula (I) below, where R ¹ and R ² are independently selected from saturated or unsaturated hydrocarbon groups that adequately contain from 8 to 30 carbon atoms, or R ¹ and R ² together with the -COC- moiety they can form a 5- to 6-membered ring, optionally being replaced by Inãís “coriTo groups hydrocarbons with up to 30 carbon atoms.

OO li li ₂ (I) R ¹ - C - O - C - R ²

Examples of suitable acid anhydrides include alkyl and alkenyl succinic anhydrides, for example, octadecyl succinic anhydride, isooctadecyl succinic anhydride, n-hexadecenyl succinic anhydride, succinic dodecenyl anhydride, succinic anhydride, succinic anhydride, succinic anhydride, succinic anhydride, succinic anhydride, succinic anhydride 2-decenyl-succinic and 1-hexyl-2-octenyl-succinic anhydride. Examples of suitable acid anhydrides further include the compounds in US Patent descrevedos ^s s. 3,102,064; 3,821,069; 3,968,005; 4,040,900; 4,522,686; and Re. 29,960, which are incorporated by reference.

The cellulose-reactive sizing agent according to the invention may contain one or more acid anhydrides, for example, one or more alkyl and / or succinic alkenyl anhydrides. Generally, the acid anhydride of the present invention is liquid at room temperature.

The dispersion according to the invention contains a dispersant, or dispersant system, comprising an electronic polyelectrolyte and an organic compound containing nitrogen. When used in combination, these compounds are effective as a dispersant for the acid anhydride sizing agent although anionic polyelectrolyte and nitrogen-containing organic compound may not be effective as a dispersant when used alone. Preferably, the dispersion is anionic, that is, the dispersion, or dispersion system, has a general anionic charge.

The anionic polyelectrolyte according to the invention can be selected from organic and inorganic compounds and can be derived from natural or synthetic sources. Anionic polyelectrolyte has two or more groups

anionics that can be of the same type or different types. Examples of suitable anionic groups, that is, groups that are anionic or made anionic in an aqueous phase, include silanol, aluminosilicate, phosphate, phosphonate, sulfate, sulfonate and sulfonic and carboxylic acid groups as well as their salts, usually warm or metal salts. alkaline (geically sodium). Anionic polyelectrolytes can be water-soluble, for example, linear and branched anionic polyelectrolytes, or dispersible in water, for example, cross-linked and / or particle anionic polyelectrolytes. Preferably, the water dispersible and / or particle anionic polyelectrolytes are colloidal, i.e., in the colloidal particle size range. The colloidal particles suitably have a particle size of from 1 nm to 100 nm, preferably from 2 to 70 nm and more preferably from 2 to 40 nm. Water dispersible and particle anionic polyelectrolytes may contain aggregated and / or non-aggregated particles.

Examples of suitable organic anionic polyelectrolytes include anionic polysaccharides such as starches, guar gums, celluloses, chitin, chitosans, glycans, galactans, glucans, xanthan gums, mannans and dextrins. Additional examples of suitable organic anionic polyelectrolytes include synthetic anionic polymers such as condensation polymers, for example, naphthalene-based and melamine-based polyurethanes and polymers, for example, condensed naphthalene sulphonates and polymers based on melamine-sulfonic acid and addition polymers of vinyl prepared from ethylenically unsaturated monomers including anionic or potentially anionic monomers, for example, acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid, vinyl sulfonic acid, styrene sulfonate and hydroxylalkyl acrylates and methacrylates, optionally copolymerized with nonionic ethylenically unsaturated monomers, for example, acrylamide, alkyl acrylates, styrene and acrylonitrile as well as derivatives of such moomers, vinyl esters and the like.

Examples of additional suitable organic anionic polyelectrolytes include water-soluble branched polymers and water-dispersible crosslinking polymers obtained by polymerizing a monomer mixture comprising one or more anionic or potentially ethylenically unsaturated monomers and, optionally, one or more other ethylenically monomers unsaturated, in the presence of one or more cross-functional cross-linking agents. The presence of a polyfunctional crosslinking ayeule in the monomer mixture makes it possible to prepare branched polymers, slightly crosslinked polymers and highly crosslinked polymers that are dispersible in water. Examples of polyfunctional crosslinking agents include compounds having at least two ethylenically unsaturated bonds, for example, N, N-methylene-bis (meth) acrylamide, polyethylene glycol di (meth) acrylate, N-vinyl (meth) acrylamide, divinylbenzene, trialylammonium and N-methylalyl (meth) acrylamide salts; compounds having an ethylenically unsaturated bond and a reactive group, for example, glycidyl (meth) acrylate, acrolein and methylol (meth) acrylamide; and compounds having at least two reactive groups, for example, dialdehydes such as glyoxal, diepoxy compounds and epichlorohydrin.

Organic anionic polyelectrolyte generally has a degree of anionic substitution (DAS) of 0.01 to 1.4, suitably from 0.1 to 1.2 and preferably from 0.2 to 1.0. Anionic polyelectrolyte can contain one or more cationic groups as long as it has a general anionic charge. The molecular weight of the anionic polyelectrolyte can vary within wide ranges; generally the molecular weight is above 200 and suitably above 500, while the upper limit is generally 10 million and preferably 2 million.

Examples of suitable inorganic anionic polyelectrolytes include anionic siliceous materials, for example, anionic silica-based materials prepared from silicic acid and smectite clays. Generally, these anionic polyelectrolytes have negative silanol, aluminosilicate or hydroxyl groups. Examples of suitable inorganic anionic polyelectrolytes include polysilicic acid, polysilicates, polyaluminiosilicates, colloidal silica-based particles, for example, silica particles, aluminated silica (modified with aluminum) and aluminiosilicate, polyis microgels10

silicate, polyaluminiosilicate microgels, silica gels and precipitated silica, smectite clays, for example, montmorillonite, bentonite, hectorite, beidelite, nontronite and saponite. Preferred anionic polyelectrolytes include silica-based materials, for example, colloidal silica-based particles.

Q with organic acid containing nitrogen acid with the invention is an amine or its quaternary ammonium. Suitable nitrogen-containing organic compounds include primary, secondary and tertiary amines and their quaternary ammonia. Organic compounds containing suitable nitrogen also include monoamines, diamines and polyamines and their quaternary ammonia. Suitable quaternary ammonia include protonated, alkylated, arylated and alkarylated amines of the types mentioned above, which can be formed by reacting the amines with, for example, acids, for example, hydrochloric acid, and methyl chloride, dimethyl sulfate and chloride benzyl. In a preferred embodiment of the invention, the nitrogen-containing organic compound is an amine or its quaternary ammonium having one or more hydroxyl groups. Preferably, one or more hydroxyl groups are present in a terminal portion of one or more substituents of the compound containing nitrogen, that is, an amine terminated in a hydroxyl group or its quaternary ammonium.

Examples of nitrogen-containing organic compounds include the following amines and their quaternary ammonia: diethylene triamine, triethylene tetramine, hexamethylene diamine, diethyl amine, dipropyl amine, diisopropyl amine, cyclohexylamine, pyrrolidine, guanidine, triethyl amine, monoethanol amine, 2 -methoxyethyl amine, aminoethylethanol amine, alanine and lysine. Additional examples of suitable nitrogen-containing organic compounds include choline hydroxide, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide. Preferred nitrogen-containing organic compounds include triethanol amine and its quaternary ammonia.

The molecular weight of the nitrogen-containing organic compound can vary within wide limits. In a preferred embodiment of the invention, the molecular weight of the amine or its quaternary ammonium is less than 180, suitably up to 170 and preferably up to 160. The molecular weight

Ζlar is generally at least 30. As mentioned here, the molecular weight of a quaternary ammonium amine means the molecular weight of the cationic part of the quaternary ammonium compound, meaning that the anionic part of the quaternary ammonium compound is not included in the given molecular weights5 above. For nitrogen-containing organic compounds that are selected from amines and their quaternary ammoniums having one or more hydroxyl groups, the molecular weights can be greater, for example, less than 500 and generally less than 300, although the molecular weights mentioned above are also suitable for such compounds.

In the present aqueous dispersion, or emulsion, the acid anhydride can be present in an amount from about 0.1 to about 50% by weight, suitably from 0.1 to about 30% by weight and preferably from about 1 to about 20% by weight, based on the weight of the aqueous dispersion. Anionic polyelectrolyte is generally present in an amount of up to about 100% by weight, generally from 0.1 to 15% by weight, suitably from 0.5 to 10% by weight and preferably from to from 1 to 7% by weight, based on the weight of the acid anhydride. The nitrogen-containing organic compound can be present in an amount of up to 20% by weight, generally from 0.1 to

15% by weight, suitably from 0.5 to 10% by weight and preferably from 1 to 7% by weight, based on the weight of the acid anhydride. In addition to acid anhydride, anionic polyelectrolyte and nitrogen-containing organic compound, additional compounds may optionally be present in the dispersion. Examples of such compounds include mo25 no-, di- and polyanionic and non-ionic surfactants and dispersing agents, stabilizers, extenders and preserving agents such as, for example, hydrolyzed acid anhydrides, for example, hydrolysed alkyl and alkenyl acid anhydrides as above mentioned, preferably hydrolyzed alkenyl succinic anhydrides, for example, hydrolyzed acid anhydrides in the form of carboxylic acid derivatives and / or carboxylic acid ester, anionic surfactants such as phosphate esters, such as ethoxylated phosphate esters, alkyl sulphates, sulphates and phosphates, alkylaryl sulfates, sulfonates and O G ..

'1 λ:'

.....

Λ ’'' phosphates, for example, sodium lauryl sulphonate and ethoxylated phosphate isotridecyl alcohol. If present, the content of such additional compounds in the dispersion can be from 0.1 to 15% by weight, suitably from 1 to 10% by weight and preferably from 2 to 7% by weight , based on the weight of the acid anhydrideTágua is also present in the provision and can constitute the remainder of the dispersion up to 100% by weight.

The dispersion according to the invention can be produced by forming a mixture containing the acid anhydride, anionic polyelectrolyte and organic compound containing nitrogen as defined above and dispersing the mixture in the presence of water. The dispersion components can be mixed in any order, but preferably the anionic polyelectrolyte and the nitrogen-containing organic compound are mixed and diluted with water to the appropriate concentration, and then the acid anhydride is dispersed in them. The mixture can be dispersed using suitable dispersion equipment providing a sufficient degree of dispersion, for example, a static mixer providing relatively low shear forces. The obtained dispersion contains droplets of acid anhydride generally having a droplet size from 0.1 to 10 pm in diameter.

The aqueous sizing dispersions according to the invention can be used in a conventional manner in the production of paper using any types of cellulosic fibers and they can be used both for surface sizing and internal sieving. The term papei, as used herein, is intended to include not only paper, but all types of cellulosic products in foil and weft including, for example, paper and cardboard. The cellulosic suspension and the finished paper may also contain mineral fillers, and generally the content of cellulosic fibers is at least 50% by weight, based on dry cellulosic suspension or finished paper. Examples of mineral fillers of conventional types include kaolin, Chinese clay, titanium dioxide, gypsum, talc and natural and synthetic calcium carbonates such as chalk, ground marble and precipitated calcium carbonate. The present invention also relates to a process for the production of paper where the present aqueous sizing dispersion is either added to a suspension

aqueous cellulosic or applied to a cellulosic sheet or web. Suitably the amount of cellulose-reactive sizing agent or added to the cellulosic suspension to be drained in a grid to form paper or applied to the surface of a cellulosic sheet or web as a surface / generally sticking on the sizing press, is from from 0.01 to 1.0% by weight, based on dry cellulosic suspension and optional fillers, preferably from 0.05 to 0.5% by weight, where the dosage is mainly dependent on the quality of the pulp or paper to be glued and the desired gluing level.

The aqueous sizing dispersions according to the invention are particularly useful in the manufacture of paper from an aqueous cellulosic suspension which has a high conductivity. The conductivity of the suspension that has the water removed from the grid can be within the range of from 0.3 mS / cm to 10 mS / cm. According to the present invention, good results can be achieved when the conductivity is at least 2.0 mS / cm, notably at least 3.5 mS / cm, particularly at least 5.0 mS / cm and still at least 7, 5 mS / cm. Conductivity can be measured using standard equipment such as, for example, a WTW LF330 instrument supplied by Christina Berner. The values referred to above are appropriately determined by measuring the conductivity of the cellulosic suspension that is fed to or present in the headbox of the paper machine or, alternatively, by measuring the conductivity of the white water obtained by withdrawing water from the suspension. High conductivity levels mean high levels of salts (electrolytes) that can be derived from materials used to form the stock, various additives introduced into the stock, fresh water supplied to the process, etc. In addition, the salt content is generally higher in processes where white water is extensively recirculated, which can lead to considerable accumulation of salts in the water circulating in the process.

Chemical agents conventionally added to the cellulosic suspension in papermaking such as retention aids, aluminum compounds, dyes, moisture resistant resins, abrasive agents ii

optical brighteners, etc., can, of course, be used in conjunction with the present dispersion. Examples of aluminum compounds include alum, aluminates and polyaluminium compounds, for example, polyaluminium chlorides and sulfates. Examples of suitable retention aids include cationic polymers / anionic inorganic materials in combination with organic polymers, for example, bentonite in combination with cationic polymers, silica-based sols in combination with cationic polymers and cationic and anionic polymers. Particularly good sizing can be obtained when using the dispersion of the invention in combination with retention aids comprising cationic polymers. Suitable cationic polymers include cationic starch, acrylate-based and acrylamide-based polymers, polyethyleneimine, polyamines, polyamidoamines and poly (diallyldimethylammonium) chloride and combinations thereof. Preferred retention aids include cationic starch-based polymers and cationic acrylamide.

In a preferred embodiment of the invention, dispersions are used in combination with a retention system comprising at least one cationic polymer and an anionic sificious material, for example, particles based on silica or bentonite. It is possible to premix one or more components of the present dispersion with a retention aid, for example, an anionic siliceous material, before introducing the mixture then obtained in the cellulosic suspension. In this way, the present aqueous sizing dispersion can be prepared shortly before its introduction into the cellulosic suspension by bringing the acid anhydride and nitrogen-containing organic compound into contact with an anionic polyelectrolyte such as, for example, an aqueous siliceous material , a sol based on silica or bentonite paste.

The invention is further illustrated in the examples that follow, which, however, are not intended to limit it. Parts and% refer to parts by weight and% by weight, respectively, unless otherwise stated.

Example 1

Aqueous dispersions according to the invention were prepared by dispersing alkenyl succinic anhydride (ASA) based on a fraction

of olefin comprising isohexadecenyl anhydride and isooctadecenyl succinic in the presence of a mixture of anionic polyelectrolyte and amine in a static hash tube mixer.

Aqueous dispersions used for comparison in this and additional examples 5 were prepared in a similar manner, that no amines, no colloidal silica, high molecular weight amines and / or amines having no hydroxyl groups were used.

The anionic polyelectrolyte used in this example was colloidal silica (Eka NP 590) in the form of an aqueous sol having a SiO ₂ content of 8.1% by weight and containing silica particles with a specific surface area of 850 m ² / g that were surface-modified with aluminum. The amine used in this example was triethanol amine (TEA) having a molecular weight of 149.

The anionic polyelectrolyte and the amine were mixed in the presence of water to form a mixture that was pumped at one end of the tube in a flow of 3.17 l / min and concentrated ASA was pumped from the side of the tube in a flow of 0.167 l / min The pressure drop in the mixing unit was 0.34 MPa (3.4 bar). The obtained dispersion had an ASA content of 5% by weight, anionic polyelectrolyte content (in this example, SiO ₂ content) of

5.0% by weight, based on ASA, and amine content ranging from 0 to 2.0% by weight, based on ASA.

Dispersions 1 to 4 were prepared, as shown in Table 1, where the SiO ₂ and amine contents given are based on ASA.

Table 1

Dispersion C ^s SiO ₂ (%) ASD (%) 1 5 0 2 5 0.5 3 5 1.0 4 5 2.0

The particle size of the ASA droplets was measured in a

Malvern Mastersizer Microplus after diluting the dispersions with water to an ASA content of 0.5% by weight. The results are shown in the Table, · ÍJÓ

2. D (v 0.1), D (v0.5) and D (v 0.9) mean that 10, 50 and 90% of the particles, respectively, had a smaller diameter than the given size.

Table 2

Particle Size (pm) whistling D (v0.1) D (v 0.5) D (v 0.9) 1 0.43 4.64 12.42 2 0.82 2.32 6.88 3 0.50 1.78 5.40 4 0.59 1.43 5.30

As can be seen from Table 2, the dispersions according to the present invention, Dispersions Ns. 2 to 4, resulted in smaller particle sizes on the dispersion used for comparison, Dispersion N ^s

1.

The gluing efficiency was assessed by preparing sheets for hand according to the standard method SCAN-C26: 76 and gluing was measured as Cobb-60 values according to the standard method Tappi T441.

Sheets of paper were prepared according to a process where the dispersions were added to an aqueous cellulosic suspension comprising recycled pulp having a fiber concentration of 0.5 g / l, conductivity of 0.7 mS / cm and a pH of around 7 , 0. The dispersions were added in amounts of 0.5.1.0 and 1.5 kg / t, calculated as ASA and based on the weight of dry cellulosic suspension. A retention system was used comprising 6 kg / t of cationic potato starch (Perlbond970) and 0.5 kg / t of silica sol (Eka NP 442), calculated as dry substances in dry cellulosic suspension.

Cobb-60 values were measured and the results are shown in Table 3. A lower Cobb value means that less water was absorbed and better bonding was achieved.

N ² of the Dispersion Cobb-60 0.5 kg / t 1.0 kg / t 1.5 kg / t 1 164 144 95 ΐ .....-..... ^L 142 ----- 42— J ^L - 2S - 3 145 38 26 4 48 24 21

As can be seen from Table 3, the dispersions according to the present invention, Dispersions N ² s. 2 to 4, resulted in improved bonding efficiency over the dispersion used for comparison,

Dispersion N ^s 1.

Example 2

The dispersions were prepared and the sizing efficiency of the dispersions was evaluated according to the general procedures of Example 1, except that varied silica content was used and the amine content was constant. The dispersions had an ASA content of 5% by weight, based on the weight of the dispersion. Table 4 shows the results.

Table 4

N ² of the Dispersion SiO ₂ (%) ASD (%) Cobb-60 (1 kg / t) 5 0 2 29 6 1 2 25 7 3 2 23 8 4 2 21 9 5 2 25

As can be seen from Table 4, the dispersions according to the present invention, Dispersions N ² s. 6 to 9, resulted in improved collating efficiency over the dispersion used for comparison, N ² Dispersion 5.

Example 3

The dispersions were prepared and evaluated according to the general procedures of Example 1. Comparisons of dispersions were made in aqueous cell suspensions having increased conductivity through the addition of calcium chloride. The conductivity of the suspensions was measured using a Christian Berner WTW LF330 instrument. The results are shown in Table 5.

Table 5

N ² of the Dispersion WING (%) SI2 (%) TEA (%) Conductivi- dade mS / cm Cobb-60 0.5 kg / t 1.0 kg / t 1.5 kg / t 10 5 0 2 4 128 123 117 11 5 5 2 4 126 108 48 10 5 0 2 8 146 141 135 11 5 5 2 8 125 105 47

As can be seen from Table 5, the dispersion according to the present invention, Dispersion N ² 11, showed sizing efficiency considerably better than the dispersion used for comparison, Dispersion N ² 10, when the conductivity of the suspension was increased .

Example 4

Dispersions were prepared and evaluated according to the general procedures of Example 1, except that different amines were used. The obtained dispersion had an ASA content of 5% by weight, an S1O2 content of 5.0% by weight, based on ASA, and an amine content of 2.0% by weight, based on ASA.

The amines used were triethanol amine (TEA) having a molecular weight of 149, diethylene triamine (DETA) having a molecular weight of 103, a fractionated coconut fatty amine (FCA) having a molecular weight of about 200 and a dimethylammonium chloride dihydrogen tallow (DTDMAC) having a molecular weight of about 530.

Particle sizes are shown in Table 6.

, -χ, / ί? '

Table 6

Dispersion C ^s Dispersion Amine Particle Size a (pm). D (v0.1) D (v 0.5) D (v 0.9) 12 DTDMAC 0.34 2.05 9.79 13 FCA ....... 0.41 - ----- 33, ^ - 211.0 - J 14 DETA 0.13 0.41 1.86 15 TEA 0.11 0.27 0.67

The results of gluing efficiency are shown in Tabe

Ia 7.

Table 7

N ² of the Dispersion Dispersion Amine Cobb-60 0.5 kg / t 1.0 kg / t 1.5 kg / t 12 DTDMAC 106 44 29 13 FCA 114 83 39 14 DETA 87 26 23 15 TEA 51 26 21

As can be seen from Tables 6 and 7, the dispersions according to the present invention, Dispersions N ² s. 14 and 15, which contained amines having a molecular weight of less than 180 (Dispersions N ^and s. 14 and 15) and having hydroxyl groups (Dispersion N ^s 15), resulted in smaller particle size and considerably improved bonding efficiency. on the dispersions used for comparison, Dispersions N ^s s. 12 and 13. This also means that less energy was required to free surfaces in accordance with the present invention.

Example 5

The dispersions were prepared and evaluated according to the general procedures of Example 1, except that different anionic polyelectrolytes were used. The dispersion obtained had an ASA content of 5% by weight, a SiO ₂ content of 5.0% by weight, based on the ASA and a triethanol amine content of 0 or 2.0% by weight, based on the ASA. The anionic polyelectrolytes used are shown in Table 8.

Table 8

Polyelectrolyte Anionic description Brand registered Size of Primary Particle (nm) THE Colloidal Aium Silica Eka NP 590 3 B Colloidal Silica Eka BMA-0 5.5 Ç Colloidal Silica Bindzil 50/80 34 D Bentonite Hydrocol flake structure AND Bentonite Opazil AV flake structure

The bentonites were made into pulp (5% by weight of

bentonite) and stored for 5 days in order to achieve sufficient swelling and delamination.

Particle size was determined and stability was assessed. Stability was measured 2 hours after preparation. If still stable after 24 hours, the particle size was determined again. The term sep. it means separation. The results are shown in Table 9.

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Table 9

D (v 0.5) (24 h) » 0.27 0.27 r- CM θ ' 1 0.23 t 0.25 Stability/ Separation (2 h) Sep. small. φ > « LU Sep. small. Stable Sep. small .. Stable Separation Stable Separation I Stable ! Particle Size (pm) D (v 0.9) 8.29 0.83 69 * 9 09 * 0 CM CO 0.70 10.67 99 * 0 38.8 0.64 D (v 0.5) 1.21 0.27 1.26 0.33 1.99 0.27 0.25 LO XT CM 0.27 the ~ > Q 0.21 O O 0.25 0.16 0.27 0.10 0.20 O O 14.32 Amine content (%) 1 CM CM CM r CM 1 CM Polyelectrolyte Anionic < < ω CD O O Q Q LU LU N ^and Dispersion CD CO O) O CM CM 22 CO CM 24 tn CM

The results of the gluing efficiency assessment are shown in Table 10.

Table 10

N ^{5 * * * 9 10 * * * * 15 * * * * 20} of the Dispersion Polyelectrolyte Anionic Amine Content (%) "----- - eobb-60 - - - 0.5 kg / t 0.75 kg / t 1.0 kg / t 16 THE - 128 103 64 17 THE 2 89 44 29 18 B - 129 62 33 19 B 2 91 40 33 20 Ç - 116 102 66 21 Ç 2 128 45 31 22 D - 120 112 91 23 D 2 88 34 28 24 AND - 122 127 120 25 AND 2 99 41 29

As can be seen from Tables 9 and 10, the dispersions according to the present invention, Dispersions Ns. 17, 19, 21, 23 and 25, which both contained anionic polyelectrolyte and nitrogen-containing organic compound, showed better sizing efficiency, better stability and resulted in a smaller particle size over the dispersions used for comparison, N ^s s dispersions. 16, 18, 20, 22 and 24, which did not contain any organic nitrogen-containing compounds.

Example 6

The dispersions were prepared and particle size and sizing efficiency of the dispersions were evaluated according to the general procedures of Example 1, except that different surfactants and varying levels of surfactants were used. The anionic polyelectrolyte used was colloidal silica (Eka NP 780) in the form of aqueous sol having a SiO ₂ content of 7.5% by weight and containing silica particles with a specific surface area of about 900 m ² / g which were modified with aluminum. The amine used was triethanol amine (TEA). The dispersion obtained had a

5% by weight ASA, 5.0% by weight SiO ₂ based on ASA, and

amine content of 2.0% by weight, based on ASA.

No surfactant was incorporated into Dispersion N ^and 26. ASA hydrolyzate was incorporated as surfactant into Dispersions N ^Q s. 27 and 28. The surfactant used in Dispersion N ^and 29 was phosphate ester (poly (oxy-1,25 ethanediyl) cdfã ^: isotridecir-omega-hydroxyphosphate) 7 The Teotes of the surfactant-in- - dispersions were based on ASA. The results of the particle size measurements are shown in Table 11.

Table 11

Dispersion C ^s Surfactant in Dispersal TeordeTen- soative (%) Particle Size (pm) D (v0.1) D (v 0.5) D (v 0.9) 26 - - 0.33 4.67 14.53 27 Htdrolysed ASA 1 0.29 2.42 7.63 28 Hydrolyzed ASA 2.5 0.12 0.45 1.83 29 phosphate ester 1 0.17 1.05 4.16

Bonding efficiency of the dispersions was evaluated and comparisons of the dispersions were made in an aqueous cellulosic suspension comprising 70% pulp (80/20 birch / pine kraft) and 30% load (CaCO ₃ ).

Table 12

N ^and Dispersion Conductivity mS / cm Cobb-60 0.5 kg / t 0.75 kg / t 1.0 kg / t 26 0.4 91 84 70 27 0.4 81 69 54 28 0.4 72 48 31 29 0.4 76 49 41 26 0.7 87 78 75 27 0.7 81 64 54 28 0.7 76 47 31 29 0.7 73 52 37

As can be seen from the results presented in the

Tables 11 and 12, N ^Q s Dispersions. 27, 28 and 29 containing a surfactant resulted in a smaller particle size and showed better bonding efficiency than the dispersion containing no surfactant.

Example 7 - The dispersions of Examples 6 were evaluated in terms of sizing efficiency when using aqueous cellulosic suspensions comprising unbleached Kraft pulp having varying conductivities. The results are shown in Table 13.

Table 13

Dispersion C ^s Conductivity mS / cm Cobb-60 0.5 kg / t 0.75 kg / t 1.0 kg / t 26 0.4 100 72 37 27 0.4 86 42 27 28 0.4 40 28 23 29 0.4 49 28 22 28 0.7 44 27 22 26 4.0 97 100 76 27 4.0 89 52 28 28 4.0 44 27 23 29 4.0 102 98 76

As can be seen from Table 13, Dispersions N ^and s. 27, 28 and 29 containing a surfactant showed better bonding efficiency than dispersions containing no surfactant, Dispersion N ^and 26.

Claims (10)

1. Aqueous dispersion of cellulose-reactive sizing agent, characterized by: contain an acid anhydride, an anionic polyelectrolyte and an organic compound containing nitrogen which is an amine or its quaternary ammonium having a molecular weight of less than 180 and / or having one or more hydroxyl groups; wherein the acid anhydride can be present in an amount of from 0.1 to 50% by weight, based on the weight of the aqueous dispersion; wherein the anionic polyelectrolyte is generally present in an amount of up to 100% by weight, based on the weight of the acid anhydride; and in which nitrogen-containing organic compound can be present in an amount of up to 20% by weight, based on the weight of the 15 acid anhydride. Aqueous dispersion according to claim 1, characterized in that the nitrogen-containing compound has a molecular weight of up to 170. Aqueous dispersion according to either of Claims 1 and 2, characterized in that the nitrogen-containing compound has a weight 20 molecular up to 160. Aqueous dispersion according to any one of claims 1 to 3, characterized in that the nitrogen-containing compound has one or more hydroxyl groups. Aqueous dispersion according to claim 4 characterized by one or more hydroxyl groups being present in a terminal position of one or more substituents of the nitrogen-containing compound. An aqueous dispersion according to any one of claims 1 to 5, characterized in that the nitrogen-containing compound is an amine. Aqueous dispersion according to any one of claims 1 to 5, characterized in that the nitrogen-containing compound is a quaternary ammonium. Petition 870160077350, of 12/20/2016, p. 5/11 Aqueous dispersion according to any one of claims 1 to 7, characterized in that the nitrogen-containing compound is diethylene triamine, triethylene tetramine, hexamethylene diamine, diethyl amine, dipropyl amine, diisopropyl amine, cyclohexylamine, pyrrolidine, guanidine, triethanol amine, monoethanol amine, diethanol amine, 2-methoxyethyl amine, aminoethanol amine, alanine, lysine, choline hydroxide, tetramethyl ammonium hydroxide or tetraethyl ammonium hydroxide. Aqueous dispersion according to any one of claims 1 to 8, characterized in that the anionic polyelectrolyte is an inorganic material. Aqueous dispersion according to claim 9, characterized in that the anionic polyelectrolyte is a siliceous material. Aqueous dispersion according to claim 10, characterized in that the anionic polyelectrolyte is bentonite. 12. Aqueous dispersion according to claim 10, characterized in that the anionic polyelectrolyte comprises particles based on silica. Aqueous dispersion according to any one of claims 1 to 12, characterized in that the acid anhydride is succinic isooctadece anhydride, succinic isooctadecyl anhydride, succinic n-hexadecenyl anhydride, succinic dodecenyl anhydride, succinic anhydride, succinic anhydride, succinic anhydride succinic, 1-octyl-2-decenyl-succinic anhydride or 1-hexyl-2-octenyl-succinic anhydride. 14. Aqueous dispersion, according to any of claims 1 to 13, characterized by the dispersion further comprising an anionic surfactant. An aqueous dispersion according to claim 14, characterized in that the anionic surfactant is hydrolyzed acid anhydride. An aqueous dispersion according to claim 1, characterized in that the acid anhydride can be present in an amount from 0.1 to 30% by weight, based on the weight of the aqueous dispersion. 17. Aqueous dispersion according to claim 1, character 870160077350, of 12/20/2016, p. 6/11 termed by the acid anhydride may be present in an amount of 1 to 20% by weight, based on the weight of the aqueous dispersion. 18. Aqueous dispersion according to claim 1, characterized in that the anionic polyelectrolyte is present in an amount of 0.1 5 to 15% by weight, based on the weight of the acid anhydride. 19. Aqueous dispersion according to claim 1, characterized in that the anionic polyelectrolyte is present in an amount of 0.5 to 10% by weight, based on the weight of the acid anhydride. 20. Aqueous dispersion according to claim 1, characterized by the anionic polyelectrolyte being present in an amount from 1 to 7% by weight, based on the weight of the acid anhydride. 21. Aqueous dispersion according to claim 1, characterized in that the nitrogen-containing organic compound can be present in an amount of 0.1 to 15% by weight, based on the weight of the anhydride 15 acid. 22. Aqueous dispersion according to claim 1, characterized in that the nitrogen-containing organic compound can be present in an amount of 0.5 to 10% by weight, based on the weight of the acid anhydride. 23. Aqueous dispersion according to claim 1, characterized in that the nitrogen-containing organic compound can be present in an amount of 1 to 7% by weight, based on the weight of the acid anhydride. 24. Method for the preparation of an aqueous dispersion, as defined in claim 1, of cellulose-reactive sizing agent, characterized in that it comprises dispersion of an acid anhydride in an aqueous phase in the presence of an anionic polyelectrolyte and an organic compound containing nitrogen which is an amine or its quaternary ammonium having a molecular weight of less than 180. 25. Method for the preparation of an aqueous dispersion, as defined in claim 1, of cellulose-reactive sizing agent, characterized in that it comprises dispersion of an acid anhydride in a Petition 870160077350, of 12/20/2016, p. 7/11 aqueous phase in the presence of an anionic polyelectrolyte and an organic compound containing nitrogen which is an amine or its quaternary ammonium having one or more hydroxyl groups. 26. Use of the aqueous dispersion of cellulose-reactive sizing agent, as defined in any one of claims 1 to 23, characterized in that it is for sizing or surface sizing in paper production. 27. Process for the production of paper, characterized by comprising the addition of an aqueous dispersion of reactive sizing agent 10 with cellulose to an aqueous cellulosic suspension and removal of water from the suspension obtained in a grid, or by applying an aqueous dispersion of cellulose-reactive sizing agent to the surface of a cellulosic sheet or web, where the dispersion is an aqueous dispersion sizing agent reactive with cellulose from 0.01 to 1.0% by weight, with 15 based on the dry cellulosic suspension and optional fillers, where the dosage is mainly dependent on the quality of the pulp or paper to be glued and the desired glue level, as defined in any of claims 1 to 23. 28. Process according to claim 27, characterized by the 20 aqueous cellulosic suspension having a conductivity of at least 2.0 mS / cm. 29. Process according to claim 27, characterized in that the dispersion is preferably an aqueous dispersion of cellulose-reactive sizing agent of 0.05 to 0.5% by weight, based on the dry cellulosic suspension and optional fillers. Petition 870160077350, of 12/20/2016, p. 11/11